Note: Descriptions are shown in the official language in which they were submitted.
i~ 21~0S48
1-- ,
D E S C R I P T I O N
The invention relates to a method of sanitary cleaning by
means of a sanitary cleaner in liquid or solid form
containing organic substances inhibiting microbial action in
a quantity of at least about 0.5 g/kg sanitary cleaner, the
usual lime-dissolving water-soluble acids, organic substances
promoting micrabial action, which are resistant-against the
lime-dis~solving water-soluble acid, in a quantity of at least
mg/kg of sanitary cleaner, and optionally further
additives, wherein the germs degrading the organic substance
~ of the water are promoted in their action after diluting or
-~ 20 flushing, and to the sanitary cleaner for implementing said
method.
Prior art as described above results from the International
- Patent Application PCT/EP 90/01718~. It shows the advantage
- 2~5 that, ~on~the one hand, the desirable inhibition of microbial
~ action develops in;the first active phase of a sanitary
- cleaner, such as e.g. in a toilet bowl, and, on the other
hand, ~the degradation efficiency of the microflora of the
waste water (in the ~second active ph~se) is not disturbed. In
this respect, said prior art is therefore superior to a
sanitary cleaner according to DE-OS 25 32 432. Said sanitary
cleaner is effective in the first phase of action only, e.g.
in a toilet bowl. Its effectiveness does not extend to the
second phase of action. It is available in tablet form and
serves chiefly for removing calcareous residues, citric acid
being used as lime solvent.
:~
- 2140~8
In the sanitary cleaner in accordance with the PCT/EP
90/01718 it was found that it is desirable to increase its
effectiveness in the second phase of action. Prior art,
neither according to US-Patent 4 013 579 nor to DD 241 747,
does not give any suggestions as to that desirable improve-
ment. US-Patent 4 013 579 describes acid cleaning agents
which mandatorily contain furancarboxylic acids or their
derivatives. They are intended to remove soilings sticking to
objects. US-Patent 4 013 579 does not attribute a double
function to the furancarboxylic acids or their derivatives,
which show a high toxicity, as achieved in the prior art
method according to PCT/EP 90/01718 with simultaneous use of
germa-inhibiting and germ-promoting substances as described
at the beginning. The group of compounds of furancarboxylic
acids or their derivatives, which are termed "FCA" in the US-
Patent 4 013 579 is to replace oxalic acid hitherto used in
the corresponding prior art. As opposed thereto, the FCA are
supposed to be handled easier and safer because they do not
show a comparable high toxicity. At any rate, they are still
very toxic all the same. The invention, as described in the
following, aims in particular at not to be forced to use such
toxic agents in the sanitary cleaner. Their incorporation
means that, in the said second phase of action already
mentioned, the inhibition of microbial action is not removed,
but due to the toxicity of the FCA present, the growth of the
microorganisms, desired there, is excluded or at least
undesirably reduced. The DD 241 747 refers to an agent for
cleaning and disinfecting toilet flushing water tanks and
basins which is intended to prevent the formation of cal-
careous residues. There is no hint~ of improving themicrobacterial degradation of organic substances in the waste
water. Compa~atively complex compounds such as fatty
alcohols, ethylene propylene copolmers and alkylphenol
-~ polyglycolethane are used which additionally pollute the
waste water.
l`; 21~0548
It was an object of the invention to further improve the
initially described prior art so that the desired inhibition
of microbial action is maintained in the first phase of
action, as e.g. in a toilet basin, and, on the other hand,
the degradation action of the microflora of the waste water
(in the second phase of action) is further improved.
The above object is accomplished according to the invention
in that the sanitary cleaner contains, as germ-promoting
organic substance, an open-chain or cyclic compound of the
formula (I) R1R2N-CO-NR3R4, in which R1 through R4 are pre-
sent each independently from one another in open-chain form
or cyclic form and may have the following meanings:
hydrogen, a low alkyl group having 1 to 4 carbon atoms, a
cycloalkyl group having 3 to 6 carbon atoms, an aryl group in
form of a phenyl or naphthyl residue, an aralkyl group having
7 to 18 carbon atoms, an alkylaryl group having 7 to 18
carbon atoms or a heterocyclic group having~ 2 to 5 carbon
atoms and containing O, S or N.
Also the following urea derivatives are intended to be within
the sc`ope of the above formula (I):
R1R2N CO-N~ . CN CO N~) and R1~- NR2
~; In Formula (I), the respective residues R1, R2, R3 and R4 are
preferably hydrogen because the respective basic compounds
are commercially available or easier to produce. Within the
scope of the invention, the substituents as stated in the
above definition of the invention are especialIy suitable. As
low alkyl groups having 1 to 4 carbon atoms are herein
considered the methyl- ethyl-, n-propyl-, i-propyl- and the
various isomers of the butyl group. Among the cycloalkylic
groups having 3 to 6 carbon atoms there are in particular the
cyclopropyl-, cyclobutyl-, cyclopentyl- and the cyclohexyl
residue, among the aralkyl group having 7 to 18 carbon atoms
there are in particular the benzyl- and the phenethyl group,
,~'
~1~05~8
among the alkylaryl group having 7 to 18 carbon atoms there
is in particular the tolyl group, and among the heterocyclic
group having 2 to 5 carbon atoms, there are in particular
such, in whose heterocyclic ring there is at least one
oxygen, sulfur, or N-Atom. As suitable examples may be cited
the radicals of the oxirane, tetrahydrofuran, dioxan and
pyran. Principally, the compounds of formula (I) may be
employed also in form of their salts or other precursors
which may enhance solubility. In certain cases only this may
lead to the desired solubility in the sanitary cleaner
according to the invention. Therefore compounds may
principally be used which set free compounds of formula (I)
or allow to develop their effectiveness in the aqueous medium
only. The following statements of quantities refer always to
the compounds of formula (I) as such or to their portion
within the suitable derivatives or compounds.
In addition to the mentioned compounds of the formula (I),
other organic substances promoting microbial action may be
added which are known from the international patent
application PCT/EP 90/01718. Other known organic substances
promoting and organic substances inhibiting microbial action
have certain properties in common. So they are, as in
- particular also urea and urea derivatives, suitable within
the scope of the invention, sufficiently resistant against
organic acids or their salts within the usual temperature and
pH-ranges.
As organic substances inhibiting microbial action may be
considered in particular acid organic substances or their
salts or suitable derivatives and ethereal oils. Natural
organic substances which inhibit microbial action are
preferred. Acid organic substances referred to are in
particular aromatic, aliphatic, alicyclic and/or heterocyclic
carboxylic acids or their salts, in particular in the form of
alkali or alkaline-earth salts or also suitable derivatives
:~ thereof. Moreover, the acid organic substances for developing
:
2140548
the desirable inhibition of microbial action should be
sufficiently water-soluble. In certain cases, the carboxylic
acid itself may be little water-soluble, however the
appropriate salt thereof may be well water-solu~le and
suitable. Among the specially suitable aliphatic carboxylic
acids are particularly the lower carboxylic acids having 1 to
7 carbon atoms, such as above all formic acid, acetic acid,
propionic acid, caproic acid, malonic acid and oxalic acid as
well as various fatty acids having 6 to 12 carbon atoms, such
as sorbic acid or undecylenic acid, if they are usable in the
form of suitable water-soluble salts. Fatty acids having more
than 12 carbon atoms are not suitable as a rule because they
- themselves are not water-soluble, neither does the plurality
of their salts meet the requirement of water-solubility.
Butyric acid which is to be counted among the lower fatty
acids is not recommendable on account of its unpleasant
smell. Suitable derivatives of the above carboxylic acids are
- hydroxy acids such as glycolic acid, tartaric acid and citric
acid as well as oxo acids such as acetoacetic acid and
20 ~ pyruvic acid. Particularly useful are also sufficiently
water-soluble aromatic carboxylic acids such as benzoic acid,
salicylic acid and also other phenolcarboxylic acids.
Of especial advantage are also ethereal oils. As microbicidal
ethereal oils are to be considered: Oil of thyme, citrus oil,
eucalyptus oils, c~love oil, origanum oil, rosemary Qil,
cinnamon oil, elecampane oil, camphor oil, conifer oils and
- fennel oils. Oil of thyme is especially preferred. In their
places may be used also the effective substances contained
therein. Examples of substances inhibiting microbial action,
which are contained in ethereal oils are: Thymol, carvacrol,
terpineol, cineole and fenchone. The ethereal oils are water-
~-~ insoluble, but they may be used in sanitary cleaners as germ-
inhibiting substances together with appropriate, emulsifiers
- 3~5 or solubilizer:; in particular those which are not harmful to
~ the environment, just as the water-insoluble vitamins.
r ~ ,
' ~;
21405~8
Virtually all surfactants (~tensides~) may be used as
solubilizers for the above group of substances. The selection
of the most appropriate solubilizers for aqueous systems is
carried out according to the HLB System and must be found
individually for every ethereal oil by experiment.
Solubilizers having HLB values in the range of 12 to 18 are
especially suitable for ethereal oils. Especially such
solubilizers are to be selected which are described in Rcmpps
Chemie-Lexikon, 8th edition, vol. 3, page 2399. By principle,
the following surfactants, devided into groups, are
appropriate surfactants: anionic surfactants: fatty alkyl
sulfonates such as Na-laurylethersulfate; cationic
surfactants: quaternary ammonium compounds such as dodecyl
dimethyl ammoniumchloride, betaine derivatives such as fatty-
acid amidopropyl dimethyl amino acetic acid betaine; non-
ionogenic emulsifiers or solution intermediaries: fruit acid
esters of mono di glycerides such as citric acid esters,
polyoxyethylene glycerol fatty-acid esters such as
i
polyoxyethylene glycerol monolaurate having 30 mol of
ethylene oxide.
Especially advantageous organic acids which inhibit microbial
action were found to be formic acid, acetic acid, propionic
~ ac-id, benzoic acid or simple derivatives of benzoic acid,
-~ 25 sorbic acid, also in the form of suitable water-soluble salts
thereof such as sodium and potassium salts. It is evident
that the lime-dissolving organic acids such as citric acid,
in general differ from the organic acids which inhibit
- .
microbial actionj in terms of their effects in a suitable
sanitary cleaner. In certain cases,-an organic acid may be
lime-dissolving on the one hand and moreover provide an
inhibition of microbial action. In general, it is preferred
to use such an acid which has a special lime-dissolving
effect, and on the other hand such an organic compound which
provides an especially high inhibition of microbial action.
.
~1~ 0~ '~ 8
The germ-inhibiting organic substances are contained in the
sanitary cleaner according to the invention, irrespective of
their being in powdered, granulated or liquid form, at least
in a quantity of approximately 0.5 g/kg sanitary clea~ner, and
preferably in a quantity of about 0.5 to 150 g/kg sanitary
cleaner, in particular in a quantity of l to 80 g/kg sanitary
cleaner, and especially preferred in a quantity of about 2 to
7 g/kg sanitary cleaner.
The concentration of the germ-inhibiting organic substances
in the first phase of action is preferably adjusted such that
their concentration therein or in the basin to be cleaned
amounts to at least approximately the minimum inhibiting
concentration (MHK) and not over approximately 200 times the
minimum inhibiting concentration (MHK). It is especially
- preferred that the concentration of the germ-inhibiting
organic substances in the first phase of action amounts to at
least about the double and not~ over about 50 times, in
particular approximately 30 times, the minimum lnhibiting
concentration.
Within the scope of the invention there may be used as germ-
promoti~ng substances in addition to the mentioned compounds
of formula~(I), preferably also aminoacids and/or orotic acid
or suit~able salts or derivatives thereof as well as vitamins.
The aforementioned derivatization must not go so far as to
adversely affect the germ-promoting action desired. The
pre~ferred amino acids are alanine, arginine, asparagine,
aspartic acid, citrulline, cysteine, cystine, glutamine,
- 30 glutamic acid~, glycine~, ~histidine, hydroxyproline`, iso-
leucine, leucine, lysine, methionine, ornithine, phenyl-
alanine, proline, serine, threonine, tryptophan, tyrosine and
~- valin. Among the especially suitable vitamins including their
provitamins count L-ascorbic acid, salts of ascorbic acid
-~ ~35 especially the Ca-salt, L-ascorbyl plamitate, (+)-biotin, b-
carotene, cholecalciferol, cyanocobalamin, dihydrofolic acid,
dehydroascorbic acid, ergocalciferol, folic acid,
, ~ .
.~,
..,
21~0548 ~l
.: . 9
--8--
hydroxycobalamin, niacinamide, nicotinic acid (niacin), D-
panthenol, D-pantothenic acid, pyridoxal, pyridoxal-5-phos-
phate, pyridoxamine, pyridoxamine-5'-phosphate, pyridoxine,
pyridoxine phosphate, riboflavin, riboflavin-5'-phosphate,
rutin, rutin salts, especially rutin sulfate, tetrahydrofolic
acid, thiamin, thiamin nitrate, thiamine phosphoric esters,
thiamine pyrophosphate, a-tocopherol, ~-tocopherol, a-
tocopheryl acetate, a-tocopheryl quinone, a-~ocopheryl phos-
phate, a-tocopheryl succinate, vitamin A acetate, vitamin A
aldehyde, vitamin A alcohol, vitamin ~ acid, vitamin B4
(adenine), vitamin Kl, vitamin K4, vitamin P and vitamin U
(methionine S-methylsulfonium chloride). In case that the
vitamins have acid or basic groups it is generally possible
to use also appropriate salts thereof.
The invention permits a hygienic cleaning of sanitary instal-
lations without disturbing the microbial degradation of the
organic substances in the waste water. Such apparently con-
tradictory properties could be accomplished by introducing
the described germ-inhibiting or germicidal agents into the
sanitary cleaner according to the invention in such a
concentration, that their concentration during application in
the therefor provided first phase of action, such as in
toilet bowls, lies above the minimum inhibition concentration
(MHK). This "minimum inhibition concentration" is a well
known technical term. At the same time the germ-promoting
organic substances are introduced into the product in a
concentration, i.e. in an amount that after the usual dilu-
tion of the medium of the first phase, they subsequently
exert a growth-promoting action upon the microorganisms on
entering into the waste water.
On using the sanitary cleaner according to the invention,
which may be present e.g. in powdered, granular or aqueous
form, same may be diluted with little water e.g. in the
toilet bowl. There the sanitary agents develop their germ-
inhibiting or germicidal effects, whereas the germ-promoting
5 ~ 8
substances initially remain inactive. After flushing the
toilet bowl subsequent to the action of the sanitary cleaner,
the concentration of the germ-inhibiting organic substances
is reduced below the MHK value; thus they become ineffective.
The germ-promoting organic substances are apportioned in
their concentration in the sanitary cleaner according to the
invention so that they even promote the activities of the
waste water germs which degrade the organic substance after
the flushing or a strong dilution; thus they accelerate the
biological purification of the waste water or at least do not
disturb it.
The quantity of germ-promoting substances in the form of
compounds of the formula (I) in the sanitary cleaner accord-
ing to the invention is not critical. In every individualcase there must be tested which minimum concentration has to
be used. As quantitative minimum is to be considered a quan-
tity of approximately 10 mg/kg sanitary cleaner, in particu-
lar the range of about 10 mg/kg to about 50 g/kg sanitary
cleaner, in particular approximately 1 g to 15 gtkg sanitary
cleaner of the compounds (~) and/or (II).
As a quantitative guideline for the further germ-promoting
~ organic substances which can be incorporated in addition to
the already men~ioned germ-promoting organic substances in
the form of the compounds of formula (I~ there may be
mentioned a minimum quantity of 10 mg/kg, and in particular
of about 10 to 1000 mg/kg. As further germ-promoting organic
substances the mentioned substances may be considered,
preferably aminoacid, vitamins, orotic acid and p-
aminobenzoic acid. Of practical importance is a mixture of
about 2 mg biotin, about 20 mg nicotinic amide, about 10 mg
thiamin, about 10 mg p-aminobenzoic acid, about S mg
pantothenic acid, about 50 mg pyridoxamin, about 2 mg
cyanocobalamin (vitamin B12) and about 10 mg orotic acid,
such mixture being present preferably in 1 kg of sanitary
cleaner. For optimizing the effects of the germ-promoting
~, :
2140S4~
-10-
organic substances desired, same are selected, if they are
used as a mixture, qualitatively and quantitatively with
respect to the respective environment.
Further known additives may be incorporated into the sanitary
cleaner according to the invention, such as e.g. performes,
coloring agents, biological foamers. The foamer used was
found to be in particular a water-soluble protein substance
with a concomitant germ-promoting action, such as water-
soluble whey protein. The preferred concentration of a water-
soluble protein substance is approximately 2 to 30 g, and
most preferably approximately 5 to 10 g to approximately 1 kg
powdery sanitary cleaner or approximately 1000 ml liquid
sanitary cleaner. Naturally the invention does not preclude
the addition of other substances known in prior art, which r
should be selected keeping in mind ~he maintenance of the
advantages of environmental compatibility etc. as far as
possible.
The particular advantage of the invention resides in the fact
that the respiratory activity of the microflora in municipal
waste waters may be enhanced to a surprising extent as shown
by ~the following examples. Thus, the sanitary cleaner in
accordance with the invention does lead to a sensible reduc-
tion ~af environmental pollution because its disinfecting
- I effects derive from degradable natural substances, i.e. the
-~ lime-dissolving water-soluble acid, the germ-inhibiting
organic substances and the germ-promoting organic substances
in the form of the compounds according to formula (I), in
particular in the form of urea, can be of natural origin. The
sanitary cleaner in accordance with the invention is
therefore especially propitious for the environment, meets
the requirements placed and meets very much the desires of
the consumers with increasing environmental conscience. It
may therefore be used in many fields of applications, so in
the whole field of sanitary cleaning such as in particular in
toilet bowls, urinaries, bath tubs, bidets, wash basins and
21~0S~8
shower tubs. This listing of application possibilities is not
exhaustive.
In the following, the invention is further illustrated with
reference to three formulation examples:
Example 1 (aqueous product / comparative example in accor-
dance with PCT/EP 90/01718):
Citric acid 175 g .
Sodium hydroxide 22 g
. Formic acid 10 ml
Sodium benzoate 2 g `
Potassium sorbate 2 g
Mixture of vitamins
and amino acids (see below) 0.5 g `.
Thickener (xanthan) 5 g
soluble whey protein 10 g
The above mixture was filled up with water to make 1000 ml.
The mixture of vitamins and amino acids was composed as
follows: 2 mg biotin, 20 mg nicotinic amide, 10 mg thiamine,
10 mg p-aminobenzoic acid, 5 mg pantothenic acid, 50 mg ~
pyridoxamine, 2 mg cyanocobalamin (vitamin B12) and 10 mg .
orotic acid.
Example 2 (invention)
Citric acid 175 g
Sodium hydroxide 22 g
Formic acid 10 ml
Sodium benzoate 2 g
Potassium sorbate 2 g
Urea 1 g
Thickener (xanthan) 5 g
soluble whey protein 10 g
This mixture was filled up with water ta make 1000 ml.
21io5~8
-12-
Examples 3 and 4 (invention)
The formulation of example 2 was modified in that the quan-
tity of urea was changed. It amounted to 2g in exam~le 3 and
to 5g in example 4.
Comparative experiments:
The positive effects of the sanitary cleaner of the above
examples 1 through 4 upon the microflora of the waste water
were to be examined. The respiratory activity of the micro-
flora in municipal sewage water was measured in order to
check if the mentioned sanitary cleaners ~ere able to promote
the flora and if they are easily degradable. Fresh sewage
water was added to the products of the examples 1 through 4
above in three concentrations. After 24 hours the carbon
dioxide formed was measured. The dry substance contents and
the pH values of the products were measured in parallel.
Test results
pH values and dry substances of the products
.
Product pH value dry substance (~
1 2.90 5.8
2 2.78 6.0
3 2.83 6.2
4 2.75 6.4
The products differ slightly as to their pH values and dry
substances contents. Variations of the respiratory activity
of the microflora are represented in the following Table 1.
-
21~0~8
-13-
Table 1
~Respiratory activity of the sewage flora as function of the
composition of the sanitary cleaners and their concentration
in sewage water)
Product Concentrationmicrobial
of product inrespiratory
sewaqe wateractivity
(%)
(mg C02/
lOml sew.=24h)
- Control . 0 3.18
(untreated waste water)
:
- -: 20 0.1 ~ 4.06
1 0.5 :7.61
: 1.0 8.31
:
:~ 25 0.1 4.09
2 0.5 8.09
1.0 9.23
0.1 5.16
~: 3 0.5 8.35
1.0 10.36
,
0.1 5.85
4 0.5 10.11
:~ ~ 1.0 10.73
,
2140~48
-14-
The above comparative values show that the respiratory activ-
ity was noticeably enhanced due to the addition of urea as
compared with the comparative product (1). The addition of
5 g of the growth factor in form of urea in sanitary cleaner
No. 4 enhances the respiration as compared with the compara-
tive product (1) up to an average of 135 (!) ~. The addition
of urea in the shown quantities results therefore in a re-
markable enhancement of the effectivity of the waste water
flora.
***
